Charge flow and solvent dynamics in the photodissosiation of cluster ions: a nonadiabatic molecular dynamics study of I2−·Arn

Experimental studies of photodissociation in I2−·Arn clusters have shown a rapid onset of caging for n > 10 and bimodal photofragment distributions in both dissociation and recombination channels. We simulate and interpret these results using a Hamiltonian that accounts for the strong perturbation of the solute electronic structure by the solvent. The high-mass products in the recombination channel are identified with excited state recombination. The two classes of dissociation products are identified with ejection of either a neutral I atom or an I− ion from the cluster, with the latter mechanism driven by the negative polarizability of the excited electronic state.